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WO1999064485A1 - Polymeres hydro-absorbants avec des molecules creuses supramoleculaires, leur procede de preparation et leur utilisation - Google Patents

Polymeres hydro-absorbants avec des molecules creuses supramoleculaires, leur procede de preparation et leur utilisation Download PDF

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Publication number
WO1999064485A1
WO1999064485A1 PCT/EP1999/003705 EP9903705W WO9964485A1 WO 1999064485 A1 WO1999064485 A1 WO 1999064485A1 EP 9903705 W EP9903705 W EP 9903705W WO 9964485 A1 WO9964485 A1 WO 9964485A1
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Prior art keywords
polymer
cyclodextrin
weight
cyclodextrins
polymers
Prior art date
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PCT/EP1999/003705
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German (de)
English (en)
Inventor
Christoph Bruhn
Edgar Herrmann
Jörg ISSBERNER
Dagmar Kersten
Richard Mertens
Georg Werner
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Stockhausen Gmbh & Co. Kg
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Priority to AT99926461T priority Critical patent/ATE251646T1/de
Priority to CA002333131A priority patent/CA2333131A1/fr
Priority to DE59907307T priority patent/DE59907307D1/de
Priority to US09/701,564 priority patent/US6911572B1/en
Priority to MXPA00011526 priority patent/MXPA00011526A/es
Priority to AU43708/99A priority patent/AU4370899A/en
Application filed by Stockhausen Gmbh & Co. Kg filed Critical Stockhausen Gmbh & Co. Kg
Priority to EP99926461A priority patent/EP1091983B1/fr
Priority to BRPI9911077-6A priority patent/BR9911077B1/pt
Priority to DK99926461T priority patent/DK1091983T3/da
Publication of WO1999064485A1 publication Critical patent/WO1999064485A1/fr
Priority to NO20006184A priority patent/NO20006184D0/no
Priority to US10/775,185 priority patent/US6958429B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/23—Carbohydrates
    • A61L2300/232—Monosaccharides, disaccharides, polysaccharides, lipopolysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/80—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special chemical form
    • A61L2300/802—Additives, excipients, e.g. cyclodextrins, fatty acids, surfactants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249954—With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249958—Void-containing component is synthetic resin or natural rubbers

Definitions

  • the invention relates to absorbents, preferably for water and aqueous liquids, based on polymers absorbing aqueous liquids, in which cyclodextrins or cyclodextrin derivatives are bound ionically, covalently or by mechanical inclusions.
  • the commercially available superabsorbent polymers are essentially crosslinked polyacrylic acids, crosslinked starch / acrylic acid graft copolymers, crosslinked hydrolyzed starch / acrylonitrile graft copolymers, crosslinked poly (maleic anhydride-co-isobutylene) or mixtures of various aforementioned crosslinked polymers, in which the carboxyl groups are partially neutralized with sodium and / or potassium ions.
  • Polymers of this type are used, for example, in hygiene articles which can absorb body fluids such as urine or in materials for covering cables. There they absorb large amounts of aqueous liquids and body fluids, such as urine or blood, with the swelling and formation of hydrogels. It is also necessary that the amount of liquid absorbed is retained under the pressure typical of the application. In the course of the technical development of superabsorbent polymers, the requirement profile for these products has changed significantly over the years. So far, the development of superabsorbents has been particularly promoted with regard to the amount of liquid absorbed and the pressure stability.
  • crosslinked polymers based on monomers containing acid groups are obtained by using one or more pre-crosslinkers and one or more postcrosslinkers, and show previously unachieved property combinations of high retention, high absorption under pressure, low soluble fractions and rapid liquid absorption.
  • these crosslinked polymers When used in hygiene articles, these crosslinked polymers have the advantage that the excreted liquids, once absorbed by the polymer, can no longer produce skin contact. Damage to the skin, such as diaper rash, can essentially be avoided in this way. Comfort can also be increased by absorbing odor-damaging compounds.
  • Inorganic ions contain: Na + (5.9 g), K + (2.7 g), NH + (0.8 g), Ca 2+ (0.5 g), Mg 2+ (0.4 g), CT (8.9 g), PO 4 3 " (4, 1 g), SO 4 2" (2.4 g).
  • the dry content is between 50 and 72 g.
  • the volatile components of the urine include alkyl furans, ketones, lactones, pyrrole, allyl isothiocyanate and dimethyl sulfone
  • the volatile comp usually around molecules with a molecular weight below approx. 1000 g / mol, which have a high vapor pressure.
  • cavity molecules also called endohedral or concave molecules
  • guest molecules can take up other, usually smaller, so-called guest molecules and thus form a host / guest complex. This complex formation affects the chemical and physical properties of the guest and host molecules.
  • cavity-forming molecules include cyclodextrins.
  • Cyclodextrins are produced when starch is broken down by Bacillus macerans or Bacillus circulans under the action of cyclodextrin glycosyltransferase. They consist of 6, 7, 8 or 9 in a cycle ⁇ -1, 4-linked glucose units ( ⁇ , ⁇ or ⁇ , cyclodextrins). They are able to include hydrophobic guest molecules in varying amounts until saturation ("molecular encapsulation"), e.g. Gases, alcohols or hydrocarbons.
  • the applications of cyclodextrins as host molecules are extensively reported in the work of J. Szejtli (Cyclodextrin Technology, Kluwer Academic Publishers, 1988).
  • Crosslinked, water-swellable, hydrophilic bead polymers composed of hydroxyalkylcyclodextrins and crosslinking agents of the epichlorohydrin or polyepoxides type are known from US Pat. No. 5,360,899. Since these crosslinkers have a carcinogenic potential, the use of such products in hygiene articles is not possible. These cyclodextrins, which are immobilized by polymerization, are used as filling and separation material in chromatographic separation columns.
  • hydrophilic bead polymers of glycidyl or methacrylate groups bearing cyclodextrins and optionally other comonomers, such as. B. hydroxyethyl acrylate known. This too through polymerization Immobilized cyclodextrins are used as filling and separation material in chromatographic separation columns.
  • cyclodextrins in hygiene products is known from EP-A-806 195, WO 94/22501 and WO 94/22500 u. a. known.
  • the cyclodextrins are used to bind odors. If the cyclodextrins or cyclodextrin complexes are not connected to the powdery absorbent, segregation can occur during storage or transportation of the hygiene article. This means that the effectiveness of the cyclodextrins as odor-binding agents can be lost through the separation between the absorbent and cyclodextrins.
  • WO 94/22501 teaches cyclodextrin to be mixed with polyethylene glycols or other linear polymers in the "melt” or in solution and then sprayed onto the powdery absorbent.
  • linear polymers particularly preferably “thread” into the cyclodextrin cavity. This is advantageously used in supramolecular chemistry to produce, for example, rotaxanes or catenanes (cf. the documents US 5538655, G. Wenz, Angew. Chem. 1994, 106, 851).
  • the linear polymers typically have a molecular weight (M w ) of over 200.
  • Suitable polymers are, for example, also polyethylene glycol (PEG), polypropylene oxide (PEO) and Polyethyleneimine.
  • PEG polyethylene glycol
  • PEO polypropylene oxide
  • Polyethyleneimine Several cyclodextrins can be threaded simultaneously on a linear polymer chain; Harada et al. (J. Org. Chem. 58, 1993, 7524-28) report that 20 cyclodextrins can be threaded onto a polyethylene glycol with an average molecular mass of 2000 g / mol.
  • the method described in WO 94/22501 is therefore particularly disadvantageous because the cyclodextrin cavities are no longer available quantitatively for the absorption of odor-damaging compounds after this pretreatment with a polyethylene glycol.
  • the present invention was therefore based on the object of providing polymers with the ability to absorb water or aqueous liquids and with the ability to bind odorous organic compounds, such as those e.g. occur in the urine or other excretory fluids of the body, as well as processes for their production.
  • the object is achieved by providing polymers based on crosslinked, optionally partially neutralized monomers carrying acid groups, which contain cyclodextrins and / or their derivatives ionically and / or covalently bound and / or included therein.
  • the cyclodextrin component can only be extracted to a reduced extent by the liquid to be absorbed or only reduced to a reduced extent in the dry state. miscible.
  • the polymer according to the invention shows, despite the close linkage with the crosslinked absorber carrying acid groups, an excellent odor binding which is even stronger than that of unbound cyclodextrin.
  • the absorbent polymers also display very good odor binding when the cyclodextrin is fixed in the interior of the absorber. This can be demonstrated by an effective reduction in the gas concentration of odor-causing substances.
  • the polymers according to the invention are outstandingly suitable for the storage of active substances, these active substances being able to be released again in a controlled manner if necessary.
  • the shelf life of sensitive active ingredients is significantly improved by the incorporation in the absorbents according to the invention.
  • Cyclodextrins of the types ⁇ , ⁇ , ⁇ and their derivatives are suitable according to the invention.
  • the cyclodextrins have the following recurring structure
  • n different substituents are possible per unit (R1-R3), which may be the same or different.
  • Suitable derivatives are, above all, those which enable chemical linkage by ionic or covalent bond with the monomers bearing the acid groups or the corresponding polymers.
  • Covalent linkages are preferred via CC bonds, such as, for example, with cyclodextrin derivatives which have ethylenically unsaturated groups which co-exist during the polymerization of the monomers.
  • valent can be integrated into the polymer chain.
  • groups are, for example, (meth) acrylic, (meth) allyl and / or vinyl groups.
  • the cyclodextrin derivatives can be ionically bound by anionic or cationic groups, with the cationic groups being preferred. It is often advantageous if the cyclodextrin molecules are substituted several times with ionic groups.
  • anionic groups are carboxylate, sulfate and sulfonate groups.
  • cationic groups are quaternary nitrogen-containing groups.
  • Ionic cyclodextrins can be obtained by reacting cyclodextrin derivatives with reactive compounds such as e.g. Chloroacetic acid, sodium chloroacetate, maleic acid, maleic anhydride, succinic anhydride. In aqueous solution, such reaction products carry e.g. Carboxymethylcyclodextrin in the base has a negative charge due to the carboxylate grouping.
  • reactive compounds such as e.g. Chloroacetic acid, sodium chloroacetate, maleic acid, maleic anhydride, succinic anhydride.
  • reaction products carry e.g. Carboxymethylcyclodextrin in the base has a negative charge due to the carboxylate grouping.
  • Cyclodextrin derivatives to be used according to the invention with at least one nitrogen-containing heterocycle can be prepared from the teaching of DE-A-19520989, the disclosure of which is hereby introduced as a reference. Cyclodextrin derivatives which still contain a group which is active towards nucleophilic groups can thus be obtained. These derivatives can react directly with polymers, which in turn carry nucleophilic groups. Examples of nucleophilic groups are: -OH, -NH, or SH groups.
  • cyclodextrin derivatives to be used according to the invention can be obtained as in A. P. Croft and R. A. Bartsch, Tetrahedron Vol. 39, No. 9 pp. 1417-1473. They are obtained by reacting nitrogen-containing compounds which have at least one functional group which is able to react with the hydroxyl groups of the cyclodextrins to form ethers, esters or acetal groups.
  • Cationic cyclodextrins as described in Ch. Roussel, A. Favrou, Journal of Chromatography A, 704 (1995), 67-74 are particularly preferred. You will get by reacting cyclodextrin with, for example, N- (3-chloro-2-hydroxypropyl) -N, N, N-trimethylammonium chloride.
  • the cyclodextrins described in this publication have a degree of substitution of 0.2.
  • the ionic cyclodextrins which can be used according to the invention and have at least one nitrogen-containing aliphatic radical can also be prepared, for example, by the processes described in US Pat. Nos. 3740391, 4153585 and 4638058.
  • the disclosure of the aforementioned prior publications is hereby introduced as a reference.
  • Suitable monomers are: N, N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-N-N-(2-aminoethyl)-2-aminoethyl-N-N-N-N-N-N-N-N-N-N-N-N
  • N, N-Dimethylaminopropylacrylamide (DIMAPA or DJ APA quat.) are preferably used.
  • R ⁇ C2 - C4 alkylene group
  • R 3 H, Ci - C4 alkyl group
  • the average degree of substitution per anhydroglucose unit can be determined for nitrogen-containing substituents by methods known from the literature via elemental analysis, as described, for example, in US Pat. No. 5,134,127 and US Pat. No. 3,453,257 for sulfur or nitrogen-containing substituents is described. With the synthesis methods described in US 3,740,391, 4,153,585, the DS value can be varied within wide limits. 3 hydroxyl groups per anhydroglycose unit of a cyclodextrin are capable of further reactions. Therefore, the degree of substitution, for example in the case of ⁇ -cyclodextrin, can be at most between 0.05 and 3. A degree of substitution below 0.05 means that there is a mixture of unmodified cyclodextrin and chemically modified cyclodextrin.
  • the degree of substitution (DS) of the cyclodextrin derivatives is 0.005-2, preferably 0.05-1.5.
  • the cyclodextrins can contain further substituents which are not reactive towards the polymer.
  • alkylating agents such as. B. Ci to C 22 - alkyl halides, such as methyl chloride, ethyl chloride, butyl chloride, butyl bromide, benzyl chloride, lauryl chloride, stearyl chloride or dimethyl sulfate or reaction products of cyclodextrins with alkylene oxides, such as. B. ethylene oxide, propylene oxide, butylene oxide or styrene oxide.
  • the amount of cyclodextrins or their derivatives to be used according to the invention is 0.01-50% by weight, preferably 0.1-30% by weight, particularly preferably 0.5-10% by weight:
  • the known methods are suitable, such as e.g. B. bulk polymerization, solution polymerization, spray polymerization, inverse emulsion polymerization and inverse suspension polymerization.
  • the solution polymerization is preferably carried out in water as the solvent.
  • the solution polymerization can be carried out continuously or batchwise.
  • the prior art has a wide range of possible variations with regard to the concentration ratios, temperatures, type and amount of the initiators and also of the post-catalysts. Typical processes are described in the following patents, which are hereby incorporated as a disclosure of the process according to the invention:
  • Suitable acid group-containing, ethylenically unsaturated monomers are preferably aliphatic, optionally substituted C 2 -C 6), preferably C 2 -Cs carboxylic acids or sulfonic acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, vinyl acetic acid, vinyl sulfonic acid, methallylsul - Fonic acid, 2-acrylamido-2-methyl-l-propanesulfonic acid and their alkali and / or ammonium salts or mixtures thereof.
  • Acrylic acid and mixtures thereof and their alkali and / or ammonium salts are preferably used. Furthermore, it is also possible to use monomers which are only hydrolyzed to acid groups after the polymerization, such as. B. the corresponding nitrile compounds.
  • crosslinking monomers with more than one reactive group in the molecule are also polymerized. This produces partially cross-linked polymers that are no longer soluble in water, but are only swellable.
  • Crosslinking monomers are, for example, bi- or higher-functional monomers, such as. B.
  • Methylene bisacryl or methacrylamide or ethylene bisacrylamide also called allyl compounds such as allyl (meth) acrylate, alkoxylated allyl (meth) acrylate with preferably 1 to 30 mol ethylene oxide units triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxiethan, triallylamine, tetraallylethylene diamine , Allyl esters of phosphoric acid or phosphorous acid, furthermore the N-methylol compounds of unsaturated amides, such as. B.
  • methacrylamide or acrylamide and the derived ethers and esters of polyols and alkoxylated polyols with unsaturated acids such as diacrylates or triacrylates such as butanediol or ethylene glycol diacrylate, polyglycol di (meth) acrylates, trimethylolpropane triacrylate, di- and triacrylate esters , preferably with 1 to 30 mol of alkylene oxide alkoxylated (ethoxylated) trimethylolpropane, acrylate and methacrylate esters of glycerol and pentaerythritol, and also with preferably 1 to 30 mol of ethylene oxide glycerol and pentaerythritol.
  • unsaturated acids such as diacrylates or triacrylates such as butanediol or ethylene glycol diacrylate, polyglycol di (meth) acrylates, trimethylolpropane triacrylate, di- and triacrylate esters
  • Triallylamine, acrylates of polyhydric alcohols or their Alkoxylates and methallyl alcohol acrylates or their alkoxylates are used.
  • the proportion of the crosslinking comonomers is 0.01 to 3.0% by weight, preferably 0.05 to 2.0% by weight and particularly preferably 0.05 to 1.5% by weight, based on the total weight of the monomers .
  • the neutralization of the acidic monomers which may be carried out by the polymerization process according to the invention can be carried out in various ways.
  • the polymerization can be carried out directly with the acidic monomers in accordance with the teaching of US Pat. No. 4,654,039, the neutralization then taking place subsequently in the polymer gel.
  • the acid groups of the monomers are preferably neutralized to 20-95%, preferably 50-80%, even before the polymerization and are then present as sodium and / or potassium and / or ammonium salts at the start of the polymerization.
  • Sodium hydroxide solution and / or potassium hydroxide solution and or ammonia, particularly preferably sodium hydroxide solution are preferably used, the addition of sodium carbonate, potassium carbonate or sodium bicarbonate having an additional positive effect according to the teaching of US Pat. No. 5,314,420 and US Pat. No. 5,154,713.
  • This partially neutralized monomer solution is cooled before the start of the polymerization in the adiabatic solution polymerization to a temperature below 30 ° C., preferably below 20 ° C. In the other polymerization processes, the temperatures known from the prior art are maintained, as can be seen from the literature below.
  • the polymers according to the invention can optionally contain water-soluble natural or synthetic polymers as a graft base in amounts of up to 30% by weight.
  • water-soluble natural or synthetic polymers include partially or fully hydrolyzed polyvinyl alcohols, starch or starch derivatives, cellulose or cellulose derivatives, polyacrylic acids, polyglycols or mixtures thereof.
  • the molecular weights of the polymers added as the graft base must be adapted to the conditions of the polymerization conditions. For example, in the case of aqueous solution polymerization, it may be necessary to use polymers with low to medium molecular weights for reasons of the viscosity of the polymer solution, whereas this factor plays a minor role in suspension polymerization.
  • the polymerization process according to the invention can be initiated by various conditions, e.g. by radiation with radioactive, electromagnetic or ultraviolet rays or by redox reaction of two compounds, e.g. Sodium hydrogen sulfite with potassium persulfate or ascorbic acid with hydrogen peroxide.
  • a so-called radical starter such as, for example, azobisisobutyronitrile, sodium peroxydisulfate, t-butyl hydroperoxide or dibenzoyl peroxide is also suitable. It is also possible to combine several of the starters or polymerization initiators mentioned.
  • the polymers according to the invention are preferably prepared by two methods:
  • the partially neutralized acrylic acid in aqueous solution in the presence of the crosslinking agent and, if appropriate, the polymer additives is converted into a gel by free-radical polymerization, which is then comminuted and dried and ground until a powdery, free-flowing state is achieved and sieved to the desired particle size.
  • the solution polymerization can be carried out continuously or batchwise.
  • the inverse suspension and emulsion polymerization process can also be used to prepare the polymers according to the invention.
  • an aqueous, partially neutralized acrylic acid solution is loiden and / or emulsifiers dispersed in a hydrophobic, organic solvent and started the polymerization by radical initiators.
  • the crosslinkers are either dissolved in the monomer solution and are initially introduced together with it, or are added separately and, if appropriate, during the polymerization. Any polymeric graft bases that are present are added via the monomer solution or by direct introduction into the oil phase.
  • the water is then removed azeotropically from the mixture and the polymer product is filtered off and optionally dried.
  • the properties of the polymers according to the invention are improved by subsequent surface crosslinking, in particular also in their liquid absorption under pressure, so that the known phenomenon of "gel blocking" is suppressed, in which the swollen polymer particles stick together and further liquid absorption and liquid distribution in the absorption articles hinder.
  • the carboxyl groups of the polymer molecules on the surface of the polymer particles are crosslinked with crosslinking agents at elevated temperature.
  • Methods for post-crosslinking are given, inter alia, in the publications below, such as B. in DE 40 20 780, in EP 317 106 and in WO 94/9043.
  • 5,314,420, page 8, lines 3-45 can, according to the invention, all be used advantageously in combination with a crosslinking agent used during the polymerization or a combination of crosslinking agents.
  • These compounds generally contain at least two functional groups which are capable of reacting with carboxylic acid or carboxyl groups. Alcohol, amine, aldehyde and carbonate groups are preferred, crosslinking molecules with several different functions also being used. Polyols, polyamines, polyamino alcohols and alkylene carbonates are preferably used.
  • crosslinking agents is preferably used: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerol, propylene glycol, diethanolamine, triethanolamine, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, sorbitan fatty acid ester, ethoxylated sorbitan fatty acid propoxylate, panitylol fatty acid propoxylate, trimethyl ethoxylated tetraethyl tetraethyl ester, trimethyl ester toluene, , Polyvinyl alcohol, sorbitol, ethylene carbonate, propylene carbonate.
  • crosslinking agent is preferably used in an amount of 0.01 to 30 percent by weight, preferably 0.1-10 percent by weight, based on the polymer to be crosslinked.
  • the polymer After the polymerization, the polymer is dried, ground and sieved to the particle size fraction which is favorable for the particular application and then fed to the surface crosslinking. In some cases, however, it has also proven useful to add the surface postcrosslinker before the polymer gel dries or before the partially or predominantly dried polymer is comminuted.
  • a postcrosslinking to be carried out according to the invention is carried out e.g. B. described in US 4,666,983 and DE 40 20 780, which are introduced as a reference.
  • the addition of the post-crosslinking agent is often advantageously also carried out in the form of a solution in water, organic solvents or mixtures thereof, in particular when small amounts of post-crosslinking agent are used.
  • Suitable mixing units for applying the post-crosslinking agent are e.g. Patterson-Kelley mixers, DRAIS turbulence mixers, Lödige mixers, Ruberg mixers, screw mixers, plate mixers and fluidized bed mixers, as well as continuously operating vertical mixers in which the powder is mixed at high frequency using rotating knives (Schugi mixers).
  • the surface crosslinking reaction is heated to temperatures of 60 to 250 ° C., preferably to 135 to 200 ° C. and particularly preferably to 150 to 185 ° C.
  • the duration of the heat treatment is limited by the risk that the desired property profile of the superabsorbent polymer will be destroyed due to the action of heat.
  • different sieve fractions are used to process the polymers as superabsorbers, e.g. for diapers between 100 and 1000 ⁇ m, preferably between 150 and 850 ⁇ m.
  • This grain fraction is generally produced by grinding and sieving before and or after the post-crosslinking.
  • the cyclodextrins or their derivatives are used in bulk or dissolved in a solvent.
  • a preferred solvent is water, but mixtures of water and organic solvents, such as ethyl alcohol, acetone, are also used.
  • the cyclodextrin component can be added in various process stages in the preparation of the polymer according to the invention.
  • the amount of cyclodextrins or their derivatives, based on the amount of polymer, is 0.01-50% by weight, preferably 0.1-30% by weight, particularly preferably 0.5-10% by weight:
  • Cyclodextrin or its derivative is added directly to the aqueous monomer solution before it is polymerized. If the polymer according to the invention is prepared by suspension polymerization, it is also possible to introduce all or part of the cyclodextrin in the oil phase and to meter in the monomer solution. If only part of the cyclodextrin is introduced, the rest can be introduced via the monomer solution.
  • Cyclodextrin component is applied in bulk or dissolved in water and / or an organic solvent to the comminuted polymer gel, preferably by spraying and mixing.
  • Suitable mixing units for applying the crosslinking agent and the cyclodextrin component are e.g. B. Patterson-Kelley mixers, DRAIS turbulence mixers, Lödige mixers, Ruberg mixers, screw mixers, plate mixers and fluidized bed mixers, as well as continuously operating vertical mixers in which the powder is mixed at high frequency using rotating knives (Schugi mixers). It is also possible to apply the cyclodextrin component to the comminuted, surface-crosslinked polymer. For this process variant, preferably ionically modified cyclodextrins in bulk or dissolved in water and / or an organic solvent are sprayed onto the preferably pulverulent polymer and the solvent is then evaporated.
  • the cyclodextrin component in different stages of the manufacturing process in order to optimize its effect if necessary.
  • This makes it possible, for example, to polymerize an unmodified cyclodextrin already with the monomer solution and to fix an ionically modified cyclodextrin to the surface of the polymer in the course of the surface crosslinking of the polymer.
  • the process according to the invention gives end products in which the cyclodextrin or its derivative is incorporated in the synthetic polymer in such a way that the amount of cyclodextrin which can be extracted with water is significantly less than the amount actually contained in the end product.
  • the extractable proportion of cyclodextrins in the products according to the invention falls below 85% of the amount present in the product, preferably 60%, particularly preferably 45%.
  • the polymers according to the invention are suitable as absorption agents which, in comparison with powdery absorption agents without cyclodextrin or its derivative, have a better absorption of odor-damaging compounds.
  • the polymers of the invention are used, for. B. in hygiene articles, the body fluids, such as. B. can absorb urine, or in the packaging area of z. B. meat and fish products. There they absorb large amounts of aqueous liquids and body fluids, such as urine or blood, with the swelling and formation of hydrogels.
  • the polymers according to the invention are incorporated directly into the powder Structures for absorbing liquids are incorporated or previously fixed in foamed or non-foamed fabrics. Such constructions for absorbing liquids are, for example, baby diapers, incontinence products, absorbent inserts in packaging units for food.
  • the absorbents according to the invention are outstandingly suitable for the storage of active substances.
  • the shelf life of sensitive active ingredients, for example against oxidative degradation, is significantly improved by incorporation into the absorption agents according to the invention.
  • the polymers according to the invention are also used in plant breeding and pest control in agriculture.
  • plant breeding the polymers in the vicinity of plant roots ensure an adequate supply of liquid and previously stored nutrients and are able to store and release them over a longer period of time.
  • active substances can be stored individually or in a combination of several active substances in the polymers according to the invention, which are then released in a controlled manner in time and quantity.
  • cyclodextrin concentration is determined according to the following method. The method is based on the decrease in light absorption (550 nm) of an alkaline phenolphthalein solution in the presence of cyclodextrin and can be determined as described by T. Takeuchi and T. Miwa, Chromatographia 1994, 38, 453. The experimentally obtained concentration is divided by the theoretically calculated concentration. The theoretical concentration can be determined from the amount of cyclodextrin used in the powdery absorbent divided by ⁇ O. The extracted portion of cyclodextrin is thus obtained.
  • Comparative example 1 according to patent application WO 94/22500 bwz.
  • WO 94/22501 9.850 g of a commercially available powdery absorbent (Favor®, from Stockhausen GmbH) are mixed well with 0.15 g of solid .beta.-cyclodextrin (technically beta-W7-cyclodextrin, from Wacker). The extractable proportion of cyclodextrin is then determined using the test method specified.
  • Comparative Example 2 According to patent application WO 94/22500 or WO 94/22501 40 g of polyethylene glycol (Mw 3000) are melted at elevated temperature. 40 g of cyclodextrin are added and the mixture is homogenized. 9.40 g of a commercially available powdered absorbent (Favor®, Stockhausen GmbH) are sprayed with 0.6 g of the cyclodextrin / polyethylene glycol solution, thoroughly mixed and mixed on the room. temperature cooled. The extractable proportion of cyclodextrin is then determined using the test method specified.
  • a commercially available powdered absorbent Frute, Stockhausen GmbH
  • An aqueous acrylic acid solution (29.3% by weight) is mixed with 1.2% by weight / monomer of a polyglycol acrylate crosslinking agent mixture and partially neutralized to 60 mol% with stirring and cooling with 50% sodium hydroxide solution. The solution is cooled to 7-8 ° C and with nitrogen for about 20 min. bubbled. The polymerization is after
  • Krupps household Hand mixer
  • EA 27%, determined according to the specified test method
  • 50 g of the dried, ground and sieved to 150-800 mm polymer from D) are wetted with vigorous mixing with a solution of 0.5 g of ethylene carbonate, 2 g of water and 4 g of acetone in a plastic container and with a commercially available household Hand mixer (Krupps) mixed well.
  • the wetted polymer is then heated in an oven to a temperature of 180 ° C. for 30 minutes.
  • the extractable fraction with EA 8%, determined according to the test method specified, is significantly lower due to the surface crosslinking.
  • Example 1A 50 g of the bulged, dried, ground and sieved to 150-800 mm polymer from Example 1A) are mixed vigorously with a solution of 0.5 g of ethylene carbonate, 1.5 g of unmodified cyclodextrin and 8.5 g of water in one Wet the plastic container and mix well with a standard household hand mixer (Krupps). The wetted polymer is then heated in a furnace for surface crosslinking to a temperature of 175 ° C. for 25 minutes.
  • Example 1 B 50 g of the bulged, dried, ground, post-crosslinked and sieved to 150-800 mm polymers from Example 1 B) are mixed vigorously with a solution of 0.5 g of ethylene carbonate, 1.5 g of cyclodextrin derivative according to F) and 7.3 g of water are wetted in a plastic container and mixed well with a commercially available household hand mixer (Krupps). The wetted polymer is then heated in an oven to a temperature of 175 ° C. for 25 minutes in order to crosslink it on the surface.
  • Krupps household hand mixer
  • EA 40%, determined according to the specified test method.
  • CD cyclodextrin derivative Decrease in the concentration of ethylfuran in

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Abstract

L'invention concerne des polymères absorbants à base de monomères portant des groupes acide monoéthyléniquement insaturés éventuellement neutralisés partiellement, dont les surfaces sont post-réticulées, et qui présentent des cyclodextrines et/ou des dérivés de cyclodextrine liés par covalence et/ou par voie ionique et/ou inclus.
PCT/EP1999/003705 1998-06-08 1999-05-28 Polymeres hydro-absorbants avec des molecules creuses supramoleculaires, leur procede de preparation et leur utilisation WO1999064485A1 (fr)

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CA002333131A CA2333131A1 (fr) 1998-06-08 1999-05-28 Polymeres hydro-absorbants avec des molecules creuses supramoleculaires, leur procede de preparation et leur utilisation
DE59907307T DE59907307D1 (de) 1998-06-08 1999-05-28 Wasserabsorbierende polymere mit supramolekularen hohlraummolekülen, verfahren zu deren herstellung und deren verwendung
US09/701,564 US6911572B1 (en) 1998-06-08 1999-05-28 Water-absorbing polymers having supramolecular hollow molecules, method for producing them and use of the same
MXPA00011526 MXPA00011526A (es) 1998-06-08 1999-05-28 Polimeros que absorben agua que tienen moleculas huecas, un metodo para producir las mismas, y su
AU43708/99A AU4370899A (en) 1998-06-08 1999-05-28 Water-absorbing polymers with supramolecular hollow molecules, method for producing them and use of the same
AT99926461T ATE251646T1 (de) 1998-06-08 1999-05-28 Wasserabsorbierende polymere mit supramolekularen hohlraummolekülen, verfahren zu deren herstellung und deren verwendung
EP99926461A EP1091983B1 (fr) 1998-06-08 1999-05-28 Polymeres hydro-absorbants avec des molecules creuses supramoleculaires, leur procede de preparation et leur utilisation
BRPI9911077-6A BR9911077B1 (pt) 1998-06-08 1999-05-28 polìmero absorvente à base de monÈmeros portadores de grupos ácidos, monoetilenicamente insaturados, processo para a preparação e aplicação dos mesmos.
DK99926461T DK1091983T3 (da) 1998-06-08 1999-05-28 Vandabsorberende polymerer med supramolekylære hulrumsmolekyler, fremgangsmåde til deres fremstilling og deres anvendelse
NO20006184A NO20006184D0 (no) 1998-06-08 2000-12-05 Vann-absorberende polymerer som har supermolekylære hule molekyler, en fremgangsmåte for fremstilling og anvendelse av de samme
US10/775,185 US6958429B2 (en) 1998-06-08 2004-02-11 Water-absorbing polymers with supramolecular hollow molecules, method for producing them and use of the same

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DE19825486A DE19825486C2 (de) 1998-06-08 1998-06-08 Wasserabsorbierende Polymere mit supramolekularen Hohlraummolekülen, Verfahren zu deren Herstellung und deren Verwendung
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US09701564 A-371-Of-International 1999-05-28
US10/775,185 Continuation US6958429B2 (en) 1998-06-08 2004-02-11 Water-absorbing polymers with supramolecular hollow molecules, method for producing them and use of the same

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DE59915160D1 (de) 2010-06-02
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DE19825486C2 (de) 2000-07-06
ATE251646T1 (de) 2003-10-15
DE59907307D1 (de) 2003-11-13
DE19825486A1 (de) 2000-02-03
US6911572B1 (en) 2005-06-28
ATE465185T1 (de) 2010-05-15
BR9911077B1 (pt) 2009-05-05
EP1375537B1 (fr) 2010-04-21
EP1091983B1 (fr) 2003-10-08
BR9911077A (pt) 2001-02-20
AR019608A1 (es) 2002-02-27
NO20006184D0 (no) 2000-12-05
EP1375537A2 (fr) 2004-01-02
MXPA00011526A (es) 2001-06-01
DK1091983T3 (da) 2004-02-16
ES2209447T3 (es) 2004-06-16
US20040157989A1 (en) 2004-08-12

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